The major goal of this research program is to develop catalytic enantioselective transformations based on transition metal and chiral anion catalysis that will be broadly applicable to the preparation of therapeutically relevant organic molecules. Towards this end, new enantioselective reactions of carbon-carbon ?-bonds are proposed, with a major emphasis placed on the development of enantioselective sp3-C-F bond construction. Additionally, reactions that generate or employ available building blocks, such as alkenes and boronic acids, will be targeted. These methods will be exploited in the enantioselective construction of fluorinated building blocks, heterocycles and natural product analogs. Thus, we anticipate that the proposed air and moisture tolerant transformations will provide synthetic chemists and biomedical researchers with additional tools for molecular synthesis and for single enantiomer construction.